Composition for forming insulating film and method for fabricating semiconductor device

ABSTRACT

The method for fabricating a semiconductor device comprises the step of forming a first insulating film  38  of a porous material over a substrate  10 ; the step of forming on the first insulating film  38  a second insulating film  40  containing a silicon compound containing Si—CH 3  bonds by 30-90%, and the step of irradiating UV radiation with the second insulating film  40  formed on the first insulating film  38  to cure the first insulating film  38 . Thus, UV radiation having the wavelength which eliminates CH 3  groups is sufficiently absorbed by the second insulating film, whereby the first insulating film is highly strengthened with priority by the UV cure, and the first insulating film can have the film density increased without having the dielectric constant increased.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2006-093438, filed on Mar. 30,2006, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

The present invention relates to a composition for forming an insulatingfilm and a method for fabricating a semiconductor device, morespecifically, a method for fabricating a semiconductor device includinga porous insulating film, and a composition for forming a porousinsulating film.

As the integration and the density of semiconductor integrated circuitsare increased, the semiconductor devices are required to have moremulti-level structures. On the other hand, with the increasingintegration, the interconnection pitch becomes smaller, and theinterconnection delay due to increased capacitances between theinterconnections is a problem.

An interconnection delay is influenced by an interconnection resistanceand a capacitance between interconnections. The interconnection delay isexpressed byT∝CR.when the interconnection resistance is expressed by R and thecapacitance between interconnections is expressed by C. In thisexpression, when an interconnection pitch is d, an electrode area (anarea of the side surfaces of the opposed interconnections) is S, adielectric constant ∈_(r), a vacuum dielectric constant is ∈_(o), acapacitance C between the interconnections is expressed byC=∈ _(o)∈_(r) S/d.Accordingly, to decrease the interconnection delay it is effective meansto lower the dielectric constant of the insulating film.

Conventionally, as insulating materials, inorganic films as of silicondioxide (SiO₂), silicon nitride (SiN), phospho-silicate glass (PSG),etc., and organic polymers, such as polyimide, etc., have been used.However, the dielectric constant of the CVD-SiO₂ film, which is mostused in the semiconductor devices is about 4. SiOF film, which is beingstudied as a low dielectric constant CVD film, has a dielectric constantof about 3.3-3.5 but is so hygroscopic that it absorbs humidity toincrease the dielectric constant.

Recently, porous insulating film is noted as an insulating material offurther lower dielectric constant. The porous insulating film is madeporous by adding organic resin, etc. which are evaporated or decomposedto a material for forming a film having a low dielectric constant, andevaporating or decomposing the organic resin by heat for forming thefilm.

The related arts are disclosed in, e.g., Reference 1 (Japanese publishedunexamined patent application No. 2000-340557) and Reference 2 (Japanesepublished unexamined patent application No. 2004-247695).

However, the porous insulating film presently has a pore size as largeas not less than 10 nm, and when the pores are increased so as todecrease the dielectric constant, the dielectric constant increase andthe film strength decrease take place due to the humidity absorption.Resultantly, cracks are often formed in the insulating film, and theinsulating film is often broken in bonding.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a method forfabricating a semiconductor device including a porous insulating film oflow dielectric constant and high mechanical strength, and a compositionfor forming an insulating film suitable to form the porous insulatingfilm.

According to one aspect of the present invention, there is provided acomposition for forming an insulating film comprising: a siliconcompound containing Si—CH₃ bonds by 30-90%; and an organic solvent fordissolving the silicon compound.

According to another aspect of the present invention, there is provideda method for fabricating a semiconductor device comprising the steps of:forming a first insulating film of a porous material over a substrate;forming over the first insulating film a second insulation filmcontaining a silicon compound containing Si—CH₃ bonds by 30-90%; andirradiating UV radiation to the with the second insulating film formedon the first insulating film to cure the first insulating film.

According to the present invention, an insulating film containing asilicon compound containing SiCH₃ bonds by 30-90% is formed over aporous insulating film, and UV radiation is irradiated through theinsulating film to cure the porous insulating film, whereby UV radiationhaving the wavelength which eliminates CH₃ groups is sufficientlyabsorbed by the upper insulating film, whereby the porous insulatingfilm is highly strengthened with priority by the UV cure, and the porousinsulating film can have the film density increased without having thedielectric constant increased. The adhesion to the lower film can bealso increased. When the UV radiation is irradiated, the CH₃ group ofthe upper insulating film is eliminated, and the film density isincreased, whereby the film strength is increased, and the upperinsulating film can be used as the etching stopper film. Thus, ahigh-speed circuit substrate of higher reliability can be fabricated.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic sectional view of the semiconductor deviceaccording to one embodiment of the present invention, which shows astructure thereof.

FIGS. 2A-2C, 3A-3C, 4A-4B, 5A-5B, 6, 7 and 8 are sectional views of thesemiconductor device according to the embodiment of the presentinvention in the steps of the method for fabricating the semiconductordevice.

DETAILED DESCRIPTION OF THE INVENTION

A composition for forming an insulating film, a semiconductor device andthe method for fabricating the same according to one embodiment of thepresent invention will be explained with reference to FIGS. 1 to 8.

FIG. 1 is a diagrammatic sectional view of the semiconductor deviceaccording to the present embodiment, which shows a structure thereof.FIGS. 2A to 8 are sectional views of the semiconductor device accordingto the present embodiment in the steps of the method for fabricating thesame.

First, the composition for forming the insulating film according to thepresent embodiment will be explained.

The composition for forming the insulating film according to the presentembodiment is characterized in that the composition includes a siliconcompound containing Si—CH₃ bonds by 30-90%. Containing Si—CH₃ bonds by30-90% means here that when all the bonds to Si in the compound is 100%,the content ratio of the Si—CH₃ bonds is 30-90%. The content ratio ofthe bonds can be confirmed by separating Si-2p waveform given by, e.g.,XPS measurement. The inventors of the present application confirmed thecontent ratio of the Si—CH₃ bonds with an XPS apparatus of “Axis-Hsi”from Kratos Analytical Limited.

As long as the silicon compound forming the composition for forming theinsulating film contains Si—CH₃ bonds by 30-90%, the content ratio ofthe silicon compound is not strictly limited. Such silicon compound canbe a compound having parts of R¹ and R² of polycarbosilane expressed bythe general formula:

-   -   (where R¹ and R² may be equal to each other or different from        each other and respectively represent a hydrogen atom, a        substituted or an unsubstituted alkyl group, an alkenyl group, a        cycloalkyl group or an aryl group.)        substituted with CH₃ to thereby control the content ratio of the        Si—CH₃ bonds to be in the above-described range, or a compound        having parts of R¹, R² and R³ of polysilazane expressed by the        general formula:    -   (where R¹, R² and R³ may be equal to each other or different        from each other and respectively represent a hydrogen atom, a        substituted or an unsubstituted alkyl group, an alkenyl group, a        cycloalkyl group or an aryl group.)        substituted with CH₃ to thereby control the content ratio of the        Si—CH₃ bonds to be in the above-described range.

The composition for forming the insulating film according to the presentembodiment can be used in forming insulating film for the purpose ofhighly strengthening porous insulating film. Specifically, an insulatingfilm is formed by using the composition for forming the insulating filmaccording to the present embodiment over a porous insulating film, andthe porous insulating film is made highly strengthen by UV cure.

With an insulating film formed of the composition for forming theinsulating film according to the present embodiment on a porousinsulating film, UV cure is made, whereby UV radiation of a wavelengthrange effective to cut the CH₃ groups can be sufficiently absorbed bythe upper insulating film, whereby with the low dielectric constant ofthe lower porous insulating film maintained, the strengthening of theporous insulating film by forming siloxane bonds can be advanced withpriority. The CH₃ groups are intentionally cut in the upper insulatingfilm, whereby the silicon compound can be further densified, and theupper insulating film can function as an etching stopper.

The content ratio of the Si—CH₃ bonds is not less than 30%, because whenthe content ratio is less than 30%, the UV absorption of the upperinsulating film in the UV cure is insufficient, and it is difficult tosuppress the dielectric constant increase of the porous insulating film.When the content ratio of the Si—CH₃ bonds is not more than 90%,oppositely the UV absorption is too high in the UV cure to advance thecure of the porous insulating film, and the porous insulating filmcannot have a target value of the film strength.

The content ratio of the Si—CH₃ bonds is set in the range of 30-90%,preferably in the range of 40-70%, more preferably in the range of50-60%. This is because as the content ratio of the Si—CH₃ bonds ishigher, the effect of decreasing the dielectric constant of the porousinsulating film and the effect of increasing the etching selectivity tothe porous insulating film can be enhanced, but as the content ratio ofthe Si—CH₃ bonds is higher, it is more difficult to prepare thematerials.

The process for substituting at least one of R¹-R³ of thepolycarbosilane expressed by the above-described structural formula andpolysilzane expressed by the above-described structural formula issubstituted by CH₃ groups is not specifically limited. For example, atleast one of R¹-R³ is halogenated and reacted with a Grignard reagentcontaining CH₃ groups for the substitution.

The ingredients of the composition for forming the insulating film otherthan the silicon compound containing Si—CH₃ bonds by 30-90% are notespecially limited as long as the effects of the present invention arenot impaired and can be suitably selected corresponding to ends. Forexample, solvent and various known additives can be selected.

The solvent is not especially limited and can be suitably selectedcorresponding to ends. For example, the solvent can be ethanol,cyclohexane, methyl isobutyl ketone, methyl ethyl ketone, methylcellosolve, ethyl cellosolve, octane, decane, propylene glycol,propylene glycol monopropyl ether, propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, etc. The content of thesolvent contained in the application solution after prepared is about1-50 wt %.

Then, one example of the semiconductor devices using the composition forforming the insulating film described above will be explained withreference to FIG. 1.

A device isolation film 12 for defining device regions 14 is formed on asemiconductor substrate 10. In the device region 14, a MOS transistor 24comprising a gate electrode 18 formed over the semiconductor substrate10 with a gate insulating film 16 interposed therebetween, andsource/drain regions 22 formed in the semiconductor substrate 10 on bothsides of the gate electrode 14 is formed.

Over the semiconductor substrate 10 with the MOS transistor 24 formedon, an inter-layer insulating film 26 and a stopper film 28 are formed.In the inter-layer insulating film 26 and the stopper film 28, a contactplug 35 connected to the source/drain region 22 is buried.

Over the stopper film 28 with the contact plug 35 buried in, aninsulating film 36, an inter-layer insulating film 38 and an insulatingfilm 40 are formed. The inter-layer insulating film 38 is formed of aporous material of a low dielectric constant. In the insulating film 36,the inter-layer insulating film 38 and the insulating film 40, aninterconnection 51 of a barrier metal 48 and a Cu film 50 is buried in.

Over the insulating film 40 with the interconnection 51 buried in, aninsulating film 52, an inter-layer insulating film 54, an insulatingfilm 56, an inter-layer insulating film 58 and an insulating film 60 areformed. The inter-layer insulating films 54, 58 are formed of a porousmaterial of a low dielectric constant. A via hole 66 is formed in theinsulating film 52 and the inter-layer insulating film 54 down to theinterconnection 51. In the insulating film 56, the inter-layerinsulating film 58 and the insulating film 60, an interconnection trench72 connected to the via hole 88 is formed. In the via hole 66, a contactplug 77 a of a barrier metal 74 and a Cu film 76 is buried in. In theinterconnection trench 72, an interconnection 77 b of a barrier film 74and a Cu film 76 is buried in. The contact plug 77 a and theinterconnection 77 b are formed integral with each other.

Over the insulating film 60 with the interconnection 77 b buried in, aninsulating film 78 is formed.

In the semiconductor device according to the present embodiment shown inFIG. 1, the insulating films 40, 56, 60 formed over the inter-layerinsulating films 38, 54, 58 of a porous material are formed of theabove-described composition for forming the insulating film.

Then, the method for fabricating the semiconductor device using theabove-described composition for forming the insulating film will beexplained with reference to FIGS. 2A to 8.

First, on the semiconductor substrate 10 of, e.g., silicon substrate,the device isolation film 12 for defining the device region 14 is formedby, e.g., LOCOS (LOCal Oxidation of silicon) method. The deviceisolation film 12 may be formed by STI (Shallow Trench Isolation).

Then, in the device region, in the same way as in the usual MOStransistor fabricating method, the MOS transistor 24 including the gateelectrode 18 formed over the semiconductor substrate 10 with the gateinsulating film 16 interposed therebetween, and the source/drain regions22 formed in the semiconductor substrate 10 on both sides of the gateelectrode 18 is formed (FIG. 2A).

Next, over the semiconductor substrate 10 with the MOS transistors 24formed on, a silicon oxide film (SiO₂), for example, is formed by, e.g.,CVD method.

Then, the surface of the silicon oxide film is polished flat by, e.g.,CMP (Chemical Mechanical Polishing) method to form the inter-layerinsulating film 26 of the silicon oxide film having the surfaceplanarized.

Next, on the inter-layer insulating film 26, a silicon nitride (SiN)film of, e.g., a 50 nm-thickness is deposited by, e.g., plasma CVDmethod to form the stopper film 28 of the silicon nitride film. Thestopper film 28 functions in later steps as the polishing stopper forCMP and as the etching stopper for forming the interconnection trench 46in the inter-layer insulating film 38, etc.

The stopper film 28 can be, other than silicon nitride film, SiC hydridefilm (SiC:H film), SiC hydride oxide film (SiC:O:H film), SiC nitridefilm (SiC:N film) or others. The SiC:H film is SiC film with hydrogen(H) present therein. SiC:O:H film is SiC film with oxygen (O) and H(hydrogen) present therein. SiC:N film is SiC film with N (nitrogen)present therein.

Then, a contact hole 30 is formed in the stopper film 28 and theinter-layer insulating film 26 down to the source/drain region 22 byphotolithography and dry etching (FIG. 2B).

Next, a titanium nitride (TiN) film of, e.g., a 50 nm-thickness isdeposited on the entire surface by, e.g., sputtering method to form thebarrier metal 32 of the TiN film.

Next, on the barrier metal 32, a tungsten (W) film 34 of, e.g., 1μm-thickness is formed by, e.g., CVD method.

Next, the tungsten film 34 and the barrier metal 32 are polished by,e.g., CMP method until the surface of the stopper film 28 is exposed toform the contact plug 35 of the barrier metal 32 and the tungsten film34 buried in the contact hole 30.

Next, on the stopper film 28 with the contact plug 35 buried in, an SiChydride oxide (SiC:O:H), for example, is deposited by, e.g., plasma CVDmethod to form the insulating film 36 of the SiC hydride oxide film. TheSiC hydride oxide film is a highly dense film with oxygen (O) and H(hydrogen) present therein and functions as a barrier film forpreventing the diffusion of water, etc.

Then, on the insulating film 36, the inter-layer insulating film 38 of aporous material, e.g., porous silica of, e.g., a 160 nm-thickness isformed (FIG. 3A). The porous material forming the inter-layer insulatingfilm 38 is not especially limited as long as the material has pores. Theporous material can be carbon-added silicon oxide film formed by vaporphase growth method, carbon added porous silicon oxide film having poresformed by adding a heat decomposable compound to the carbon addedsilicon oxide film, porous silica formed by spin coating method, anorganic porous film or others. In terms of controlling the pores anddensity, porous silica formed by spin coating method is most preferable.

The inter-layer insulating film 38 of porous silica is formed asexemplified below. First, the liquid of the composition for forming theporous inter-layer insulating film 38 is applied to the insulating film36 by, e.g., spin coating method to form an applied film of thecomposition for forming the insulating film. The conditions for theapplication are, e.g., 3000 rpm and 30 seconds. Next, thermal processing(soft bake) is made to semi-cure the applied film while thermallydecomposing the heat decomposable compound contained in the compositionfor forming the insulating film to form pores. Thus, the inter-layerinsulating film 38 of porous silica is formed.

In the soft bake, it is preferable to control the processing temperatureand the processing period of time so that the cross-linking degreemeasured by infrared spectroscopy is 10-90%. When the cross-linkingdegree is above 90%, the photochemical reaction by UV cure which will bemade in a later step is not smoothly advanced. When the cross-linkingdegree is less than 10%, undesirably, the insulating film therebelow isdissolved by the application solvent.

The composition for forming the porous silica can be formed by adding aheat decomposable organic compound to a polymer prepared by hydrolysisreaction or condensation polymerization reaction using as the rawmaterial, e.g., tetraalkoxysilane, trialkoxysilane, methyltrialkoxysilane, ethyl trialkoxysilane, propyl trialkoxysilane, phenyltrialkoxysilane, vinyl trialkoxysilane, allyl trialkoxysilane, glycidyltrialkoxysilane, dialkoxysilane, dimethyl dialkoxysilane, diethyldialkoxysilane, dipropyl dialkoxysilane, diphenyl dialkoxysilane,divinyl dialkoxysilane, diallyl dialkoxysilane, diglycidyldialkoxysilane, phenyl methyl dialkoxysilane, phenyl ethyldialkoxysilane, phenyl propyl trialkoxysilane, phenyl vinyldialkoxysilane, phenyl allyl dialkoxysilane, phenyl glycidyldialkoxysilane, methyl vinyl dialkoxysilane, ethyl vinyl dialkoxysilane,propyl vinyl dialkoxysilane or others. Preferably, the composition forforming the insulating film is cluster porous silica formed ofquaternary alkylamine. This is because small-sized pores can beuniformly formed. The organic compound for the heat decomposition canbe, e.g., acryl resin or others.

Then, on the inter-layer insulating film 38, the insulating film 40 of asilicon compound containing Si—CH₃ bonds by 30-90% is formed (FIG. 3B).Here, containing Si—CH₃ bonds by 30-90% means that all the bonds to Siin the compound is 100%, the content of the Si—CH₃ bonds is 30-90%. Thecontent ratio of the bonds can be confirmed by separating Si-2p waveformgiven by, e.g., XPS measurement. The inventors of the presentapplication confirmed the content ratio of the Si—CH₃ bonds with an XPSapparatus of “Axis-Hsi” from Kratos Analytical Limited.

As long as the silicon compound forming the composition for forming theinsulating film contains Si—CH₃ bonds by 30-90%, the content ratio ofthe silicon compound is not strictly limited. Such silicon compound canbe a compound having parts of R¹ and R² of polycarbosilane expressed bythe general formula:

-   -   (where R¹ and R² may be equal to each other or different from        each other and respectively represent a hydrogen atom, a        substituted or an unsubstituted alkyl group, an alkenyl group, a        cycloalkyl group or an aryl group.)        substituted with CH₃ to thereby control the content ratio of the        Si—CH₃ bonds to be in the above-described range, or a compound        having parts of R¹, R² and R³ of polysilazane expressed by the        general formula:    -   (where R¹, R² and R³ may be equal to each other or different        from each other and respectively represent a hydrogen atom, a        substituted or an unsubstituted alkyl group, an alkenyl group, a        cycloalkyl group or an aryl group.)        substituted with CH₃ to thereby control the content ratio of the        Si—CH₃ bonds to be in the above-described range.

The content ratio of the Si—CH₃ bonds is not less than 30%, because whenthe content ratio is less than 30%, the UV absorption of the insulatingfilm 40 in the UV cure to be made in a step which will be describedafter is insufficient, and it is difficult to suppress the dielectricconstant increase of the porous insulating film 38. When the contentratio of the Si—CH₃ bonds is not more than 90%, oppositely the UVabsorption is too high in the UV cure to advance the cure of the porousinsulating film, and the porous insulating film cannot have a targetvalue of the film strength.

The insulating film 40 is formed as exemplified below. First, the liquidof the composition for forming the insulating film 40 is applied to theinsulating film 36 by, e.g., spin coating method to form an applied filmof the composition for forming the insulating film. Then, thermalprocessing (soft bake) is made to semi-cure the applied film to form theinsulating film 40.

Then, UV radiation is irradiated, through the insulating film 40, to theinter-layer insulating film 38 to UV cure the inter-layer insulatingfilm 38 (FIG. 3C). The UV cure may be made in vacuum or under the normalpressure, but preferably the UV cure is made in vacuum. For the UV curein vacuum, an inert gas, such as nitrogen, argon or others, may beintroduced for the pressure adjustment and reforming. In irradiating theUV radiation, it is preferable to apply the UV radiation while beingheated at 50-470° C. This is because the cure of the porous inter-layerinsulating film 38 is accelerated, the film strength can be increasedand the adhesion to the lower insulating film (the stopper film 28) canbe increased. The temperature of the thermal processing may be constantor changed in a plurality of steps.

In the UV cure, because of the insulating film 40 of the siliconcompound containing Si—CH₃ bonds by 30-90% formed on the inter-layerinsulating film 38, part of the UV radiation having the wavelength rangewhich eliminates CH₃ groups is absorbed by the insulating film 40 toallow only the UV radiation necessary to dehydrate and condense silanolgroups remaining in the inter-layer insulating film 38 to arrive at theinter-layer insulating film 38. Thus, the elimination of the CH₃ groupssuppresses the increase of the dielectric constant while, the filmstrength of the inter-layer insulating film 38 can be increased.

The UV cure eliminates the CH₃ groups in the insulating film 40resultantly to make the insulating film 40 highly dense. Thus, theinsulating film 40 can function as the etching stopper. The content ofthe Si—CH₃ bonds in the insulating film 40 after the UV cure wasmeasured, and all the samples had values which do not exceed 10%.

Then, a photoresist film 42 with an opening 44 exposing a region for theinterconnection of the first layer to be formed in is formed over theinsulating film 40 by photolithography.

Then, by dry etching using, e.g., CF₄ gas and CHF₃ gas, the insulatingfilm 40, the inter-layer insulating film 38 and the insulating film 36are sequentially etched with the photoresist film 42 as the mask and thestopper film 28 as the stopper to form an interconnection trench 46 forburying the interconnection 52 in the insulating film 40, theinter-layer insulating film 38 and the insulating film 36 (FIG. 4A). Theupper surface of the contact plug 35 is exposed in the interconnectiontrench 46.

Next, the photoresist film 42 is removed by, e.g., ashing.

Next, a tantalum nitride (TaN) film of, e.g., a 10 nm-thickness isdeposited over the entire surface by, e.g., sputtering method to formthe barrier metal 48 of the TaN film. The barrier metal 48 is forpreventing the diffusion of Cu into the insulating film from a copperinterconnection to be formed in a later step.

Next, a Cu film of, e.g., a 10 nm-thickness is deposited on the barriermetal 48 by, e.g., sputtering method to form a seed film (not shown) ofthe Cu film.

Next, by, e.g., electroplating method with the seed film as the seed, aCu film is deposited to form a Cu film 50 of a 600 nm-thicknessincluding the thickness of the seed layer.

Next, the Cu film 50 and the barrier metal 48 on the insulating film 40are removed by CMP method to form the interconnection 51 of the barriermetal 48 and the Cu film 50 buried in the interconnection trench 46. Theprocess for forming the interconnection 51 is called single damascenemethod.

Then, an SiC hydride oxide film of, e.g., a 30 nm-thickness is depositedon the entire surface by, e.g., CVD method to form the insulating film52 of the SiC hydride oxide film (FIG. 4B). The insulating film 52functions as a barrier film for preventing the diffusion of water andthe diffusion of the Cu from the Cu interconnection.

Next, the porous inter-layer insulating film 54 is formed on theinsulating film 52. The porous inter-layer insulating film 54 is formedby the same process for forming, e.g., the inter-layer insulating film38 described above. The film thickness of the inter-layer insulatingfilm 54 is, e.g., 180 nm.

Next, on the inter-layer insulating film 54, the insulating film 56 of asilicon compound containing Si—CH₃ bonds by 30-90% is formed (FIG. 5A).The insulating film 56 is formed by the same process for forming theinsulating film 40 described above. The film thickness of the insulatingfilm 56 is, e.g., 30 nm.

Next, UV radiation is irradiated through the insulating film 56 to theinter-layer insulating film 54 to UV cure the inter-layer insulatingfilm 54. The UV cure is for increasing the film strength of the porousinter-layer insulating film 54 and increasing the film density of theinsulating film 56 and is made in the same way as the UV cure forforming the inter-layer insulating film 38 described above.

Then, the porous inter-layer insulating film 58 is formed on theinsulating film 56. The porous inter-layer insulating film 58 is formedby the same process for forming, e.g., the inter-layer insulating film38 described above. The film thickness of the inter-layer insulatingfilm 59 is, e.g., 160 nm.

Then, on the inter-layer insulating film 58, the insulating film 60 of asilicon compound containing Si—CH₃ bonds by 30-90% is formed (FIG. 5B).The insulating film 60 is formed by the same process for forming theinsulating film 40 described above. The film thickness of the insulatingfilm 60 is, e.g., 30 nm.

Next, UV radiation is applied through the insulating film 60 to theinter-layer insulating film 58 to UV cure the inter-layer insulatingfilm 58. The UV cure is for increasing the film strength of the porousinter-layer insulating film 58 and increasing the film density of theinsulating film 60. The UV cure is made in the same way as in UV curingthe inter-layer insulating film 38 described above.

Next, a photoresist film 62 having an opening 64 exposing the region fora via hole down to the interconnection 52 to be formed in is formed onthe insulating film 60 by photolithography.

Next, by dry etching using, e.g., CF₄ gas and CHF₃ gas and with thephotoresist film 62 as the mask, the insulating film 60, the inter-layerinsulating film 58, the insulating film 56, the inter-layer insulatingfilm 54 and the insulating film 52 are sequentially etched to form thevia hole 66 down to the insulating film 60, the inter-layer insulatingfilm 58, the insulating film 56, the inter-layer insulating film 54 andthe insulating film 52 (FIG. 6). The respective insulating films can besequentially etched by the composition ratio of the etching gases, andthe pressure, etc. for the etching.

Next, the photoresist film 62 is removed by, e.g., ashing.

Next, on the insulating film 60 with the via hole 66 formed in, aphotoresist film 68 with the opening 70 exposing the region for theinterconnection 77 b of the second layer to be formed in is formed byphotolithography.

Next, by dry etching using, e.g., CF₄ gas and CHF₃ gas and with thephotoresist film 68 as the mask, the insulating film 60, the inter-layerinsulating film 58 and the insulating film 56 are sequentially etched toform the interconnection trench 72 for burying the interconnection 77 bin the insulating film 60, the inter-layer insulating film 58 and theinsulating film 56 (FIG. 7). The interconnection trench 72 is connectedto the via hole 66.

Then, the photoresist film 68 is removed by, e.g., ashing.

Next, a TaN film of, e.g., a 10 nm-thickness is deposited on the entiresurface by, e.g., sputtering method to form the barrier metal 74 of theTaN film. The barrier metal 74 is for preventing the diffusion of the Cufrom a copper interconnection to be formed in a later step into theinsulating film.

Next, on the barrier metal 74, a Cu film of, e.g., a 10 nm-thickness isdeposited by, e.g., sputtering method to form a seed film (not shown) ofthe Cu film.

Then, by, e.g., electroplating using the seed film as the seed, a Cufilm is deposited to form the Cu film 76 of, e.g., a 1400 nm-thicknessincluding the thickness of the seed layer.

Then, the Cu film 76 and the barrier metal 74 on the insulating film 60are polished off by CMP method to form integral with each other at oncethe contact plug 77 a buried in the via hole 66 and formed of thebarrier metal 74 and the Cu film 76, and the interconnection 77 b buriedin the interconnection trench 72 and formed of the barrier metal 74 andthe Cu film 76. The process for thus forming the contact plug 77 a andthe interconnection 77 b integral with each other and at once is calleddual damascene method.

Then, an SiC hydride oxide film of, e.g., a 30 nm-thickness is depositedon the entire surface by, e.g., CVD method to form the insulating film78 of the SiC hydride oxide film (FIG. 8). The insulating film 78functions as the barrier film for preventing the diffusion of water andthe diffusion of the Cu from the Cu interconnection.

Then, the above-described steps are suitably repeated as required tofrom the interconnection of the third layer (not shown), etc., and thesemiconductor device according to the present embodiment is completed.

As described above, according to the present embodiment, on the porousinsulating film, the insulating film of a silicon compound containingSi—CH₃ bonds by 30-90%, and UV radiation is irradiated through theinsulating film to the porous insulating film to cure the porousinsulating film, whereby the UV radiation having the wavelength whicheliminates CH₃ groups can be sufficiently absorbed, and the strength ofthe porous insulating film can be advanced with priority by the UV cure.Resultantly, without increasing the dielectric constant of the porousinsulating film, the film density can be increased. The adhesion to thelower film can be also increased. In the irradiation of the UVradiation, the CH₃ groups in the upper insulating film are eliminated,and the film density is increased, whereby the film strength isincreased, and the upper insulating film can be used as the etchingstopper film. Thus, a circuit substrate of higher reliability and highspeed can be fabricated.

The present invention is not limited to the above-described embodimentand can cover other various modifications.

The present invention is not limited to the structure of thesemiconductor device according to the above-described embodiment and themethod for fabricating the semiconductor device, and is applicablewidely to the fabrication of semiconductor devices including porousinsulating films. The film thickness and the materials of the respectivelayers forming the semiconductor device can be suitably changed.

EXAMPLES

The composition for forming the insulating film of porous silica wasapplied to a substrate by spin coating method, and an applied film wasformed. The application conditions were, e.g., 3000 rpm and 30 seconds.Then, soft bake is made to cure the applied film while thermallydecomposing the heat decomposable compound contained in the compositionfor forming the insulating film to form pores.

Thus, the porous insulating film of porous silica was formed. Thecross-linking degree of the thus formed porous insulating film wasmeasured by infrared spectroscopy. The cross-linking degree was 10-90%.The content of Si—CH₃ bonds in the porous insulating film was give byXPS measurement, and the content ratio was 3-60%.

Next, on the thus formed porous insulating film, an insulating film ofsilicon compound containing Si—CH₃ bonds by a prescribed content ratiowas formed by spin coating method. The content ratio of Si—CH₃ bonds waschanged to prepare 11 kinds of samples described below. The contentratios of the Si—CH₃ bonds were confirmed by an XPS apparatus of“Axis-Hsi” from Kratos Analytical Limited.

Example 1

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 30%.

Example 2

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 40%.

Example 3

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 50%.

Example 4

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 60%.

Example 5

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 70%.

Example 6

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 80%.

Example 7

The insulating film was formed with the content ratio of Si—CH₃ bondsbeing 90%.

[Control 1] The insulating film was formed with the content ratio ofSi—CH₃ bonds being 0%.

[Control 2] The insulating film was formed with the content ratio ofSi—CH₃ bonds being 10%.

[Control 3] The insulating film was formed with the content ratio ofSi—CH₃ bonds being 20%.

[Control 4] The insulating film was formed with the content ratio ofSi—CH₃ bonds being 93%.

Next, UV radiation was irradiated to the porous insulating film throughthe insulating film to make UV cure the porous insulating film, and thesamples to be measured were prepared.

The dielectric constant of the porous insulating films, the strength ofthe porous insulating films and the etching selectivity of theinsulating film to the porous insulating films were measured on the thusprepared samples.

By the fabrication method according to the embodiment described above,the interconnections and the conductive plugs were formed toelectrically serially connect 1,000,000 contact plugs, and the yieldtest of the electric connections was made. The effective dielectricconstant between the interconnections was measured.

The effective dielectric constant is a dielectric constant measured withthe porous insulating film and other insulating films being presentaround the interconnections. In this case, the effective dielectricconstant was measured with the porous insulating film of relatively lowdielectric constant and also the insulating film of relatively highdielectric constant being around the interconnections, and the values ofthe effective dielectric constant are larger than the dielectricconstants of the porous insulating film.

The result of the measurement made on the 11 kinds of samples describedabove is summarized in Table 1 and TABLE 2. TABLE 1 Solid Film TestEtching Selectivity Si—CH₃ Bond to Porous Content Dielectric StrengthInsulating [%] Constant [GPa] Film Example 1 30 2.25 15.2 1.50 Example 240 2.23 14.7 1.52 Example 3 50 2.30 15.1 1.53 Example 4 60 2.26 15.51.53 Example 5 70 2.31 14.7 1.60 Example 6 80 2.27 15.0 1.70 Example 790 2.22 15.0 1.82 Control 1 0 3.00 18.2 1.22 Control 2 10 2.90 18.0 1.38Control 3 20 2.90 17.5 1.43 Control 4 93 2.27 10.0 1.88

TABLE 2 Interconnection Test Si—CH₃ Bond Effective Content DielectricYield [%] Constant [%] Example 1 30 2.6 100 Example 2 40 2.7 98.7Example 3 50 2.6 94.7 Example 4 60 2.6 96.1 Example 5 70 2.6 96.1Example 6 80 2.7 94.7 Example 7 90 2.6 94.7 Control 1 0 3.2 51.1 Control2 10 3.2 57.6 Control 3 20 3.1 57.6 Control 4 93 2.6 71.1

As shown in TABLE 1, the content ratio of Si—CH₃ bonds of the insulatingfilm is set at not less than 30% including 30%, whereby the dielectricconstant of the porous insulating film was decreased. This is becausethe content ratio of Si—CH₃ bonds of the upper insulating film is set atnot less than 30%, whereby in the UV cure, the UV radiation having thewavelength which eliminates CH₃ groups is sufficiently absorbed by theupper insulating film, and only the UV radiation necessary to dehydrateand condense silanol remaining in the porous insulating film can arriveat the porous insulating film.

On the other hand, as the ratio of the eliminated CH₃ groups isdecreased, the film strength is a little decreased. However with thecontent of the Si—CH₃ groups being 30-90%, the decrease is small. Basedon that the film strength of the porous insulating film without theinsulating film containing Si—CH₃ bonds by 30-90% is 10.0 GPa, theeffect of improving the film strength can be found also in the range of30-90% of the Si—CH₃ bond content ratio.

As the content of Si—CH₃ bonds of the insulating film was increased, theetching selectivity to the porous insulating film could be increased.With the content of the Si—CH₃ bonds being not less than 30%, theetching selectivity to the porous insulating film was not less than 1.5,and the practical value could be realized.

As shown in TABLE 2, based on the result of the yield of the electricalcontacts, the samples whose contents of Si—CH₃ are 30-90% could havehigh yields of 94.7-100%, while the samples whose contents of Si—CH₃bonds are less than 30% or more than 90% so low as 51.1-71.1%.

The resistance of the interconnection was measured after left at 200° C.for 3000 hours. No increase of the resistance value of the samples ofExamples 1 to 7 was confirmed, but increases of the resistance value ofthe samples of Controls 1 to 4 were confirmed.

1. A composition for forming an insulating film comprising: a siliconcompound containing Si—CH₃ bonds by 30-90%; and an organic solvent fordissolving the silicon compound.
 2. A composition for forming aninsulating film according to claim 1, wherein the silicon compound is acompound having parts of R¹ and R² of polycarbosilane expressed by thegeneral formula:

(where R¹ and R² may be equal to each other or different from each otherand respectively represent a hydrogen atom, a substituted or anunsubstituted alkyl group, an alkenyl group, a cycloalkyl group or anaryl group.) substituted with CH₃ to thereby control the content ratioof the Si—CH₃ bonds to be in the above-described range.
 3. A compositionfor forming an insulating film according to claim 1, wherein the siliconcompound is a compound having parts of R¹, R² and R³ of polysilazaneexpressed by the general formula:

(where R¹, R² and R³ may be equal to each other or different from eachother and respectively represent a hydrogen atom, a substituted or anunsubstituted alkyl group, an alkenyl group, a cycloalkyl group or anaryl group.) substituted with CH₃ to thereby control the content ratioof the Si—CH₃ bonds to be in the above-described range.
 4. A method forfabricating a semiconductor device comprising the steps of: forming afirst insulating film of a porous material over a substrate; formingover the first insulating film a second insulation film containing asilicon compound containing Si—CH₃ bonds by 30-90%; and irradiating UVradiation to the with the second insulating film formed on the firstinsulating film to cure the first insulating film.
 5. A method forfabricating a semiconductor device according to claim 4, wherein in thestep of curing the first insulating film, the CH₃ groups in the secondinsulating film are eliminated by the irradiation of the UV radiation toincrease a film density of the second insulating film.
 6. A method forfabricating a semiconductor device according to claim 4, wherein in thestep of forming the first insulating film, the first insulating filmcontaining therein Si—CH₃ bonds by 3-60% is formed.
 7. A method forfabricating a semiconductor device according to claim 4, wherein in thestep of curing the first insulating film, UV radiation is irradiatedwhile being heated at 50-470° C.
 8. A method for fabricating asemiconductor device according to claim 4, wherein the step of formingthe first insulating film includes the step of applying a compositionfor forming the first insulating film to form an applied film, and thestep of semi-curing the applied film by thermal processing.
 9. A methodfor fabricating a semiconductor device according to claim 8, wherein inthe step of semi-curing the applied film, conditions for the thermalprocessing are set so that a cross-linking degree in the film is 10-90%.10. A method for fabricating a semiconductor device according to claim4, wherein the step of forming the second insulating film includes thestep applying a composition for forming the second insulating film toform an applied film, and the step of semi-curing the applied film bythermal processing.
 11. A method for fabricating a semiconductor deviceaccording to claim 10, wherein in the step of semi-curing the appliedfilm, conditions for the thermal processing are set so that across-linking degree in the film is 10-90%.
 12. A method for fabricatinga semiconductor device according to claim 4, wherein a compound havingparts of R¹ and R² of polycarbosilane expressed by the general formula:

(where R¹ and R² may be equal to each other or different from each otherand respectively represent a hydrogen atom, a substituted or anunsubstituted alkyl group, an alkenyl group, a cycloalkyl group or anaryl group.) substituted with CH₃ to thereby control the content ratioof the Si—CH₃ bonds to be in the above-described range is used as thesilicon compound.
 13. A method for fabricating a semiconductor deviceaccording to claim 4, wherein a compound having parts of R¹, R² and R³of polysilazane expressed by the general formula:

(where R¹, R² and R³ may be equal to each other or different from eachother and respectively represent a hydrogen atom, a substituted or anunsubstituted alkyl group, an alkenyl group, a cycloalkyl group or anaryl group.) substituted with CH₃ to thereby control the content ratioof the Si—CH₃ bonds to be in the above-described range is used as thesilicon compound.
 14. A method for fabricating a semiconductor deviceaccording to claim 4, wherein in the step of forming the firstinsulating film, the first insulating film is formed of porous silica.